Process for increasing receptivity to fluorescent whitening agents in resin-treated cellulosic textiles

ABSTRACT

Cellulosic textiles are converted to the soda-cellulosate which is then reacted with glycidyltrimethylammonium chloride and subsequently reacted with an N-methylolated resin formulation to obtain finished products which readily attract fluorescent whitening or brightening agents. Alternate processes which are less efficient though more economically attractive are also provided, the one simply eliminating conversion to sodacellulosate and the other mixing all ingredients in one reaction bath.

United States Patent [1 1 Berni et al.

[ 1 Oct. 21, 1975 PROCESS FOR INCREASING RECEPTIVITY TO FLUORESCENT WHITENING AGENTS IN RESIN-TREATED CELLULOSIC TEXTILES Inventors: Ralph J. Berni, Metairie; Ruth R.

Benerito, New Orleans; Mary W. Pilkington, Metairie, all of La.

The United States of America as represented by the Secretary of Agriculture, Washington, DC.

Filed: Dec. 15, 1972 Appl. No.: 315,731

Published under the Trial Voluntary Protest Program on January 28, 1975 as document no. B 315,731.

Assignee:

U.S. Cl. 8/185; 8/187; 8/DIG. 11; 117/] 39.4 Int. Cl. D06? 3/00 Field of Search 8/125, 185, 187, DIG. 27, 8/DlG. ll; 117/139.4

[56] References Cited UNITED STATES PATENTS 3,644,082 2/1972 Berni et al. 8/188 Primary Examiner-Stephen J. Lechert, Jr. Attorney, Agent, or Firm-M. Howard Silverstein; Max D. Hensley [57 ABSTRACT 36 Claims, N0 Drawings PROCESS FOR INCREASING RECEPIIVITY TO FLUORESCENT WHITENING AGENTS IN RESIN-TREATED CELLULOSIC TEXTILES A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to a process for making resintreated cotton or cotton blend fabrics more receptive to fluorescent whitening or brightening agents. Resintreated cotton, which has some of its available hydroxyl groups reacted, is notoriously unable to attract whitening or brightening agents which are common additives in modern detergent compositions. Utilization of this process will allow this deficiency in resin-treated cotton and cotton blends to be overcome.

Prior art processes involve the addition of polymer or copolymer systems which increase the substantivity (receptiveness) of the fabric for the fluorescent whitening or brightening agents. These processes are costly in that they require large add-ons of polymers which often cause unwanted side effects to the detriment of cotton and cotton blend fabric physical properties and comfort factors.

The main object of the invention is to provide a process for imparting permanent press properties to cotton and/or cotton-polyester blends without destroying the substantivity (receptiveness) of the fabric for common fluorescent whitening or brightening agents found as part of the formulation of cotton household detergents.

A summary of the invention can be given as follows: Cellulosic textiles can be made more receptive to fluorescent whitening agents by reacting the textiles in the form of sodium cellulosate in aqueous or non-aqueous media with 540% t-butanol solution of glycidyltrimethylammonium chloride (GTMAC), removing the textiles from the reaction liquor, washing, and drying. The textiles at this point contain from 0.1 to 0.6% N in the quaternary ammonium form as illustrated by the following equation:

The fabrics then are reacted in the usual manner with any of a number of N-methylol ureas and a metal salt catalyst to give high dry and wet wrinkle recovery. More specfically, the fabrics are padded usually twice with an aqueous solution containing 8 g. dimethyloldihydroxyethylene urea (DMDHEU), 0.89 zinc nitrate hexahydrate [Zn(NO -6H O] per 100 ml of solution. The fabrics are then dried at 60C for 7 minutes and cured at 130C for 10 minutes. The resultant textiles exhibit high dry and wet wrinkle recovery, high enough to give excellent permanent press ratings after repeated home launderings. More importantly, the fabrics after each laundering are substantive (receptive) to the fluorescent whitening agent present in the detergent. Fabrics treated with the same formulation without initial reaction with GTMAC are not substantive to these agents as shown by fluorescent measurements on treated fabrics. Fabrics with the GTMAC treatment had fluorescence values equal to the untreated control and always much greater than the resin control fabrics. Measurements were taken on fabric samples using a Farrand Spectrofluorometer with excitation at 400 mu and fluorescence measured at 450 mu.

An alternative method used was to employ a twobath process in which the GTMAC is twice padded on the fabric in the presence of 2ml of 40% zinc fluoroborate solution, dried at C for 7 minutes and cured at 130C for 10 minutes. The trmted fabric is washed free of excess reagents and then given a standard permanent press treatment with DMDl-IEU and Zn(NO as mentioned previously. Again the GTMAC treated fabrics gave higher fluorescent values than the resin control without loss of wrinkle recovery properties.

A third method was employed which involved a single bath treatment with GTMAC and DMDHEU. Although high levels of fluorescence could be obtained,

some loss in wrinkle recovery must be tolerated because of the poisoning or neutralization of the catalyst by the basic GTMAC.

The process utilizes glycidyltrimethylammonium chloride at levels of from 2 to 7% by weight in 100 g of aqueous or t-butyl alcohol solution. Also any number of N-methylolated urea resins such as dimethylolethylene urea, dimethyloldihydroxyethylene urea, dimethylolpropylene urea, dimethylol-S- hydroxpropylene urea, dimethylolmethyl carbamate, dimethylolethyl carbamate, and the like which are known to impart permanent press properties to cotton or cotton-blended textiles, at levels of from 6% to 20% by weight in I00 g of aqueous solutions.

Any Lewis acid catalyst can be employed to catalyze the reaction of the cellulose with the resins of this invention, including metal salts such as zinc nitrate, zinc chloride, magnesium nitrate, magnesium chloride, zinc fluoborate, and the like, and also amine hydrochlorides or any number of mineral acids at levels of from 0.2 to 2.0% per 100 g of treating solution.

Sodium cellulosate may be prepared by the method of US. Pat. No. 3,644,082.

The following examples are provided to illustrate preferred-embodiments of this invention and are not meant to be limits to the invention.

EXAMPLE 1 Cotton printcloth (10 g) was rolled and placed in a reaction chamber containing 10 other fabrics to which was added dimethylformamide (DMF) (-3 liters) for swelling purposes. The fabric was allowed to soak for 16 hours, the DMF was removed and three exchanges of absolute methanol (MeOl-l) were made to remove DMF and water from the fabric. The MeOH was removed and replaced with a 1.6 molar solution of sodium methoxide in MeOl-l. The fabric was allowed to react for minutes with dry nitrogen gas used for stirring. The sodium methoxide was then removed and the fabrics were rinsed three times in t-butyl alcohol. A small test fabric was removed at this point and the fabrics were shown to contain 1.2 meq. of Na per gram by titration with sodium hydroxide (NaOl-I) after addition of excess hydrochloric acid (HCl). The fabric was then removed and placed in a graduated cylinder containing 14.75 g glycidyltrimethylammonium chloride (GTMAC) dissolved in 200 ml of t-butyl alcohol and allowedto react 5 hours at room temperature. The fabrics were then removed from the cylindersand washed in tap water followed by 5% acetic acid'andthot tap water for 15 minutes, then rinsed in distilled water and ironed dry. After equilibration, the fabric showed a 1% add-on and a.0.15%'N content. The fabric was then twice padded to a 90% wet pick-up with a solution containing 8 g of dimethyloldihydroxyethylene urea (DMDHEU), 0.89 gof Zn(NO -6H O and 91.11 g of water The fabric then dried at 60C for 7 minutes and cured, at 160C for 3 minutes. Final nitrogen was 1.5%, a conditioned and wet crease recovery of 290 and 297 (W+F), respectively. The fabric, after a home laundering in Tide (commercial detergent which contains a whiteningagent) gave a fluorescence reading equal to that of the control cotton (0.7 vs 0.7) with excitation at 400 my. and fluorescence at 450 my. on a Farrand Spectrofluorometer. A resin-treated control given the same DMDHEU treatment without any GTMAC treatment and after laundering, gave a reading of 0.08, 10% of the untreated control. These differences remained constant after 7 home launderings as shown in the following table.

Cotton printcloth (80 was twice padded to about 90% wetpick-up in aqueous solution containing 2 g of glycidyltrimethylammonium chloride in a total volume V of 100 ml. The sample was then dried at 60C for 7 minutes and cured at 130C for 10 minutes. The fabric showed a 0.80.9% weight add-on after washing in tap water (pl-l 10.) for minutes and air drying. The fabric was then twice padded (to 90% wet pick-up) in an aqueous solution containing 10.0 g of DMDHEU, 3 ml of 1 molar Zn(NO solution in a total solution of 100 ml. The sample was then dried at 60C for 3 minutes and cured at 130C for IOminutes. The fabric was then washed in hottap water for 15 minutes, then line dried overnight. The fabric showed a weight add-on of 4.4 to 5.2%. Wrinkle recovery values were 256 and 249 (W+F), respectively, for conditioned and wet values. Fluorescent values obtained as'in Example 1 were as follows after 1 home laundering in Tide:

Reading (microamps) Untreated control cotton 0.50 DMDHEU treated 0.05 GTMAC-DMDHEU treated 0.48

EXAMPLEB Cottong printcloth (80 was twice padded to 90% wet pickup with an aqueous solution containing2 g GTMAC, 10 g DMDHEU and 4 ml of 40% Zn(BF4) solution in ml total volume. The fabric was dried 7 minutes at 60C and cured 10 minutes at C and washed 15 minutes in hot tap water followed by line drying. The fabric showed 6.68.l% add-on (average of two duplicate samples), conditioned and wet wrinkle recovery were 262 and 253 (W+F), respectively.

After a home laundering,,fluorescent readings were as follows:

microamps Untreated control 0.5 DMDHEU treated cotton I 0.08 GTMAC-DMDHEU treated cotton 0.2

In this example, the GTMAC treatment was twice as good as the resin control but not as effective as the untreated cotton.

We claim: 1

l."An improvement process for imparting to cellulosic textiles'the quality of receptivity to fluorescent whitening or brightening agents without destroying the sisting of dimethyloldihydroxyethylene urea, dimethylolethylene urea, dimethylolpropylene urea,

dimethylol-S-hydroxypropylene urea, dimethylolmethyl carbamate, and dimethylolethyl carbamate, and about from 0.3 to 2.0% of a Lewis-acid type catalyst selected from the group consisting of zinc chloride, zinc. fluoborate, zinc nitrate, magnesium chloride, and magnesium nitrate, and i e. drying and curing the reacted textile.

2. An improvement process for impartingto cellulosic textiles the quality of receptivity to fluorescent whitening or brightening agents without destroying the natural or imparted physical properties of the textiles, the process comprising:

a. reacting a cellulosic textile with an aqueous solution containing about from '2 to 7% of glycidyltrimethylammonium chloride,

b. drying and curing the reacted cellulosic textile of c.-reacting the cellulosic textile of (b) with an aqueous solution containing about from 6 to 20% of an N-methylolated resin selected from the group consisting of dimethyloldihydroxyethylene urea, dimethylolethylene urea, dimethylolpropylene urea,

dimethylol-S-hydroxypropylene urea, dimethylole methyl carbamate, and dimethylolethyl carbamate, and about from' 0.3 to 2% of a Lewis acid type catalystselected fromthe group consisting of zinc. ni-

trate, zinc chloride, zincv fluoborate, magnesium chloride, and magnesium nitrate, and d. drying and curing the reacted textile.

ous solution containing about from 6 to 20% of an N-methylolated resin selected from the group con- 3. An improvement process for imparting to cellulosic textiles the quality of receptivity to fluorescent whitening or brightening agents without destroying the natural or imparted physical properties of the textiles, the process comprising:

a. reacting a cellulosic textile with an aqueous formulation containing about from 2 to 7% of glycidyltrimethylammonium chloride, about from 6 to 20 percent of an N-methylolated resin selected from the group consisting of dimethyloldihydroxyethylene urea, dimethylolethylene urea, dimethylolpropylene urea, dimethyl-S-hydroxypropylene urea, dimethylolmethyl carbamate, and dimethylolethyl carbamate, and about from 0.3 to 2 percent of a Lewis acid type catalyst selected from the group consisting of zinc chloride, zinc nitrate, zinc fluoborate, magnesium chloride, and magnesium nitrate, and

b. drying and curing the wet impregnated textile.

4. The process of claim 1 wherein the N- methylolated resin is dimethyloldihydroxyethylene urea.

5. The process of claim 1 wherein the N methylolated resin is dimethylolethylene urea.

6. The process of claim 1 wherein the N- methylolated resin is dimethylolpropylene urea.

7. The process of claim 1 wherein the N- methylolated resin is dimethylol-S-hydroxypropylene urea.

8. The process of claim 1 wherein the methylolated resin is dimethylolmethyl carbamate.

9. The process of claim 1 wherein the N- methylolated resin is dimethylolethyl carbamate.

10. The process of claim 1 wherein the Lewis type catalyst is zinc chloride.

11. The process of claim 1 wherein the Lewis type catalyst is zinc fluoborate.

12. The process of claim 1 wherein the Lewis type catalyst is zinc nitrate.

13. The process of claim 1 wherein the Lewis type catalyst is magnesium chloride.

14. The process of claim 1 wherein the Lewis type catalyst is magnesium citrate.

15. The process of claim 2 wherein the N- methylolated resin is dimethyloldihydroxyethylene urea.

16. The process of claim 2 wherein the N- methylolated resin is dimethylolethylene urea.

17. The process of claim 2 wherein the N- methylolated resin is dimethylolpropylene urea.

18. The process of claim 2 wherein the N- methylolated resin is dimethylol-S-hydroxypropylene urea.

19. The process of claim 2 wherein the N- methylolated resin is dimethylolmethyl carbamate.

20. The process of claim 2 wherein the N- methylolated resin is dimethylolethyl carbamate.

21. The process of claim 2 wherein the Lewis type catalyst is zinc nitrate.

22. Theprocess of claim 2 wherein the Lewis type catalyst is zinc chloride.

23. The process of claim 2 wherein the Lewis type catalyst is zinc fluoborate.

24. The process of claim 2 wherein the Lewis type catalyst is magnesium chloride.

25. The process of claim 2 wherein the Lewis type catalyst is magnesium nitrate.

26. The process of claim 3 wherein the N- methylolated resin is dimethyloldihydroxyethylene urea.

27. The process of claim 3 wherein the N- methylolated resin is dimethylolethylene urea.

28. The process of claim 3 wherein the N- methylolated resin is dimethylolpropylene urea.

29. The process of claim 3 wherein the N- methylolated resin is dimethylol-S-hydroxypropylene urea.

30. The process of claim 3 wherein the N- methylolated resin is dimethylolmethyl carbamate.

31. The process of claim 3 wherein the N- methylolated resin is dimethylolethyl carbamate.

32. The process of claim 3 wherein the Lewis type catalyst is zinc chloride.

33. The process of claim 3 wherein the Lewis type catalyst is zinc nitrate.

34. The process of claim 3 wherein the Lewis type catalyst is zinc fluoborate.

35. The process of claim 3 wherein the Lewis type catalyst is magnesium chloride.

36. The process of claim 3 wherein the Lewis type catalyst is magnesium nitrate. 

1. AN IMPROVEMENT PROCESS FOR IMPARTING TO CELLULOSIC TEXTILES THE QUALITY OF RECEPTIVITY TO FLUORESCENT WHITENING OR BRIGHTENING AGENTS WITHOUT DESTROYING THE NATURAL OR IMPARTED PHYSICAL PROPERTIES OF THE TEXTILE, THE PROCESS COMPRISING: A. PROVIDING SODIUM-CELLULOSATE TEXTILE, B. REACTING THE SODIUM CELLULOSATE TEXTILE OF (A) WITH A TERTIARY BUTANOL SOLUTION CONTAINING ABOUT FROM 2 TO 7% GLYCIDYLTRIMETHYLAMMONIUM CHLORIDE, C. REMOVING EXCESS AND UNREACTED GLYCIDYLTRIMETHYLAMMONIUM CHLORIDE, AND WASHING AND DRYING THE REACTED TEXTILE, D. REACTING THE CELLULOSIC TEXILE OF (C) WITH AN AQUEOUS SOLUTION CONTAINING ABOUT FROM 6 TO 20% OF AN NMETHYLOLATED RESIN SELECTED FROM THE GROUP CONSISTING OF DIMETHYLOLDIHYDROXETHYLENE UREA, DIMETHYLOLETHYLENE UREA, DIMETHYLOLPROPYLENE UREA, DIMETHYLO-5-HYDROXYPROPYLENE UREA, DIMETHYLOLMETHYL CARBAMATE, AND DIMETHYLOLETHYL CARBAMATE, AND ABOUT FROM 0.3 TO 2.0% OF A LEWIS ACID TYPE CATALYST SELECTED FROM THE GROUP CONSISTING OF ZINC CHLORIDE, ZINC FLUOBORATE, ZINC NITRATE, MAGNESIUM CHLORIDE, AND MAGNESIUM NITRATE, AND E. DRYING AND CURING THE REACTED TEXTILE.
 2. An improvement process for imparting to cellulosic textiles the quality of receptivity to fluorescent whitening or brightening agents without destroying the natural or imparted physical properties of the textiles, the process comprising: a. reacting a cellulosic textile with an aqueous solution containing about from 2 to 7% of glycidyltrimethylammonium chloride, b. drying and curing the reacted cellulosic textile of (a), c. reacting the cellulosic textile of (b) with an aqueous solution containing about from 6 to 20% of an N-methylolated resin selected from the group consisting of dimethyloldihydroxyethylene urea, dimethylolethylene urea, dimethylolpropylene urea, dimethylol-5-hydroxypropylene urea, dimethylolmethyl carbamate, and dimethylolethyl carbamate, and about from 0.3 to 2% of a Lewis acid type catalyst selected from the group consisting of zinc nitrate, zinc chloride, zinc fluoborate, magnesium chloride, and magnesium nitrate, and d. drying and curing the reacted textile.
 3. An improvement process for imparting to cellulosic textiles the quality of receptivity to fluorescent whitening or brightening agents without destroying the natural or imparted physical properties of the textiles, the process comprising: a. reacting a cellulosic textile with an aqueous formulation containing about from 2 to 7% of glycidyltrimethylammonium chloride, about from 6 to 20 percent of an N-methylolated resin selected from the group consisting of dimethyloldihydroxyethylene urea, dimethylolethylene urea, dimethylolpropylene urea, dimethyl-5-hydroxypropylene urea, dimethylolmethyl carbamate, and dimethylolethyl carbamate, and about from 0.3 to 2 percent of a Lewis acid type catalyst selected from the group consisting of zinc chloride, zinc nitrate, zinc fluoborate, magnesium chloride, and magnesium nitrate, and b. drying and curing the wet impregnated textile.
 4. The process of claim 1 wherein the N-methylolated resin is dimethyloldihydroxyethylene urea.
 5. The process of claim 1 wherein the N-methylolated resin is dimethylolethylene urea.
 6. The process of claim 1 wherein the N-methylolated resin is dimethylolpropylene urea.
 7. The process of claim 1 wherein the N-methylolated resin is dimethylol-5-hydroxypropylene urea.
 8. The process of claim 1 wherein the N-methylolated resin is dimethylolmethyl carbamate.
 9. The process of claim 1 wherein the N-methylolated resin is dimethylolethyl carbamate.
 10. The process of claim 1 wherein the Lewis type catalyst is zinc chloride.
 11. The process of claim 1 wherein the Lewis type catalyst is zinc fluoborate.
 12. The process of claim 1 wherein the Lewis type catalyst is zinc nitrate.
 13. The process of claim 1 wherein the Lewis type catalyst is magnesium chloride.
 14. The process of claim 1 wherein the Lewis type catalyst is magnesium oitrate.
 15. The process of claim 2 wherein the N-methylolated resin is dimethyloldihydroxyethylene urea.
 16. The process of claim 2 wherein the N-methylolated resin is dimethylolethylene urea.
 17. The process of claim 2 wherein the N-methylolated resin is dimethylolpropylene urea.
 18. The process of claim 2 wherein the N-methylolated resin is dimethylol-5-hydroxypropylene urea.
 19. The process of claim 2 wherein the N-methylolated resin is dimethylolmethyl carbamate.
 20. The process of claim 2 wherein the N-methylolated resin is dimethylolethyl carbamate.
 21. The process of claim 2 wherein the Lewis type catalyst is zinc nitrate.
 22. The process of claim 2 wherein the Lewis type catalyst is zinc chloride.
 23. The process of claim 2 wherein the Lewis type catalyst is zinc fluoborate.
 24. The process of claim 2 wherein the Lewis type catalyst is magnesium chloride.
 25. The process of claim 2 wherein the Lewis type catalyst is magnesium nitrate.
 26. The process of claim 3 wherein the N-methylolated resin is dimethyloldihydroxyethylene urea.
 27. The process of claim 3 wherein the N-methylolated resin is dimethylolethylene urea.
 28. The process of claim 3 wherein the N-methylolated resin is dimethylolpropylene urea.
 29. The process of claim 3 wherein the N-methylolated resin is dimethylol-5-hydroxypropylene urea.
 30. THe process of claim 3 wherein the N-methylolated resin is dimethylolmethyl carbamate.
 31. The process of claim 3 wherein the N-methylolated resin is dimethylolethyl carbamate.
 32. The process of claim 3 wherein the Lewis type catalyst is zinc chloride.
 33. The process of claim 3 wherein the Lewis type catalyst is zinc nitrate.
 34. The process of claim 3 wherein the Lewis type catalyst is zinc fluoborate.
 35. The process of claim 3 wherein the Lewis type catalyst is magnesium chloride.
 36. The process of claim 3 wherein the Lewis type catalyst is magnesium nitrate. 